Method for providing nanocrystalline diamond coatings on gemstones and other substrates

ABSTRACT

A method to apply nano-crystalline diamond onto a selected substrate, including preparing Nanodiamond slurry of Nanodiamond particles dispersed in a medium. The medium may include a liquid or a sol-gel. The selected substrate is immersed in the Nanodiamond slurry for a predetermined period of time. Then the substrate is removed from the slurry. The substrate is then dried with a flow of inert gas. The substrate is left coated with a coating of the nanodiamond particles that are highly adherently held by van der Waals forces.

RELATED APPLICATION

This application is a divisional of application Ser. No. 12/505,648,filed Jul. 20, 2009 “Method For Providing Nanocrystalline DiamondCoatings On Gemstones And Other Substrates”, which claims the benefit ofU.S. Provisional Application No. 61/082,030, filed Jul. 18, 2008, eachof which is hereby fully incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to a process for coating utility and/ordecorative objects, with a thin film of nano-crystalline diamond for thepurpose of improving the optical and physical characteristics of saidobjects.

BACKGROUND OF THE INVENTION

Synthetic diamond films and coatings may be grown from the vapor phaseusing chemical vapor deposition (CVD) such as oxy-acetylene flamecombustion CVD, microwave plasma CVD, hot filament CVD etc. Hot filamentCVD is one of the oldest and major method of depositing high quality CVDdiamond on a large area (Ref: Growth of Diamond by sequential depositionand etching process using hot filament CVD, J. Wei and Y. Tzeng, Journalof Crystal Growth 128, (1993), 413-417). In one form, the deposition ofa synthetic diamond film on a substrate using CVD requires an activatedgas phase that is activated by high temperature and/or plasmaexcitation, with the gas phase including a carbon-containing species.Since the gas phase so described will tend to deposit both diamond andgraphite on the substrate, the gas phase must also include a speciessuch as atomic hydrogen that preferentially etches graphite. This CVDprocess also requires a substrate surface receptive to nucleation ofdiamond thereon and a temperature gradient between the gas phase and thesubstrate to drive the diamond producing species to the substrate. Otherdiamond films under the category of diamond-like carbon (DLC) consist ofa mixture of sp2 and sp3 bonds with the higher quality DLC films havinghigher percentage of sp3 bonds. Many methods for depositing DLC havebeen demonstrated, including radio frequency plasma deposition, ion beamsputter deposition from a carbon target, ion beam sputtered carbon withion beam assist, direct ion beam deposition, dual ion beam deposition,laser ablation deposition from a carbon target, and ion beam assistedevaporation of carbon [Ref: U.S. Pat. No. 5,635,245].

The use of diamond films produced by CVD processes in a decorativeapplication and use of DLC coatings on gem media are further describedin patent applications 2006/0182883 and 2003/0224167. Additionally theprior art includes various references to the application of DLC coatingsto various media such as glass or polymeric materials with a view toimprove the wear resistant characteristics or to assist in thepreservation of sharp edges (Ref: U.S. Pat. Nos. 6,277,480, 5,795,648,6,312,808, 5,635,245, 6,338,901, 6,335,086, 5,190,807 and 5,879,775).The growth of synthetic diamond films using high temperature CVDprocesses on various substrates is limited by the ability of thesubstrate to withstand high temperatures that are typically employed.

There are a multitude of non-diamond gemstones both natural andsynthetic in origin, which are colored naturally or by means of a colorenhancing treatment (Ref: Publication No. 20060182883), or clear, thatcan benefit from having a thin film diamond coating provided to thesurface of the faceted and polished gemstones all around. There arevarious other substrates which serve a commercial application such asglass windows, a utility and or decorative application such aseyeglasses and/or eyeglass frames, metal decorative objects orsubstrates or jewelry objects, watch dials and/or watch glass and watchbands that would benefit from the application of a thin film ofnano-crystalline diamond film. Many of the substrates mentioned heresuch as natural clear or colored non-diamond gemstones as well as colorenhanced gemstones cannot be exposed to high temperatures for growth ofsynthetic diamond film using CVD techniques because these materials maycrack or fracture and/or change color.

The physical characteristics that are generally accepted as being mostimportant to gemstones are hardness, refractive index, color, thermalstability, chemical stability and toughness. Hardness defines theability of a gemstone to resist scratching. Diamond is the hardestmineral with all other gemstone materials ranking in lower hardness suchas sapphire at 9 on the Mohs scale down to precious as well assemi-precious gemstones such as emerald at 7.5, topaz at 8, apatite at 5etc. Diamond, in addition its superior hardness, also possesses a veryhigh refractive index which results in diamonds having a highbrilliance.

Cubic Zirconia (CZ), the cubic crystalline form of Zirconium dioxide isa mineral that is widely synthesized for use as a diamond simulant. CZhas a high dispersive power as compared to diamond (0.06 vs. 0.044 ofdiamond) which results in increased prismatic fire in CZ that can bereadily distinguished from diamond even by the untrained eye. CZ has alower hardness at 8.5 vs. the 10 rating for diamond, as well as a lowerrefractive index than diamond. Due to CZs optical closeness to diamondincluding a high hardness, it has become a very popular low cost diamondsimulant and is consumed in large quantities in the production of lowcost jewelry.

In recent years manufacturers have sought ways to distinguish theirproduct by supposedly “improving” CZ. Coating finished CZs with a filmof DLC has been used where the resulting material is thought to providean appearance that is more diamond-like overall by supposedly quenchingthe excess fire of CZ. The improvement in visual characteristics via DLCcoating of CZ is subjective. The quality of DLC coatings and theirability to adhere to CZ is entirely dependent on the deposition processemployed. DLC films appear colorless only in very thin layers which isanother issue that has to be dealt with when coating on colorless CZ.

Yet another field in which gem media have been treated to improve theirphysical characteristics is in the area of fracture filling or clarityenhancement of such gem media. Examples include fracture filling ofdiamonds and emeralds. The filling materials that are used for diamondsare commonly of glass origin and, in the case of emeralds, the fillingsmay be of various types such as oils or polymers.

The filling of surface-reaching breaks in emeralds is a relativelycommon practice, for which various kinds of oils and a natural resinhave historically been used. Now, however, epoxy resins are replacingthe more traditional fillers such as cedar-wood oil and Canada balsam.The most widely known of these epoxy resins is sold under the brand nameOpticon. The results of a broad study by GIA, of variousfracture-filling materials found that Opticon treatment. (1) was, likethe traditional materials, best detected using magnification with avariety of lighting techniques, and (2) although somewhat more durablethan the traditional enhancements, was still altered in the course ofroutine jewelry cleaning and manufacturing processes. [Ref: FractureFilling of Emeralds: Opticon and Traditional “Oils”, Gems And Gemmology,Volume 27, Number 2, Robert C. Kammerling, John I. Koivula, Robert E.Kane, Patricia Maddison, James E. Shigley, and Emmanuel Fritsch].

The first commercially available diamond fracture-filling treatment wasdeveloped in Israel in the mid 1980s. There are currently three mainproducers of the fracture filling treatment of diamonds and all threeused proprietary formulations of a glass-like compound to fill-in thefractures that are opened to the surface by laser drilling operations.The refractive index of the filling compound is slightly less thandiamond and the treatment can be easily distinguished by a color flashthat can be observed in the filled regions when viewed at an angle. Alsothe fillings can be easily removed when the diamond is exposed totemperature above 150C or if the diamond is exposed to acids whichreadily attack the glass-like filling.

SUMMARY OF THE INVENTION

The invention solves many of the above problems. An embodiment of theinvention includes application of a nano-crystalline diamond coating toa gem material or utility or decorative object by treatment with aslurry of crystalline diamond particles without the use of harshchemicals or elevated temperatures. According to example embodiments,the invention avoids the use of methane, hydrogen and carbon monoxideand can be accomplished at reaction temperatures of from roomtemperature to 200C as compared to the prior art in which reactiontemperatures of above 900C are commonly utilized.

The invention further includes treatment with a seed slurry composed ofsub-10 nm diamond particles applied to the gem material substrate suchthat the Nanodiamond particles adhere to the substrate via van derWaal's forces. A highly adherent layer of nanodiamond particles coatingthe substrate results.

In accordance with an example embodiment of the invention, the highlyadherent layer of nanodiamond particles on the gem material ordecorative object is further stabilized by deposition of an opticallytransparent layer of DLC or layer of nitrides, oxides or oxynitrides ofvarious transition metals, or a combination thereof. The DLC layer canbe applied by known techniques.

In accordance with an embodiment of the invention, the nano-crystallinediamond layer may be applied on a faceted cubic zirconia gem materialand further stabilized with a layer of optically transparent DLC orlayer of nitrides or oxides, oxynitrides of various transition metals,or a combination thereof such that the resulting optical characteristicsclosely mimic the appearance of natural diamond. The application of thethin layer of diamond material having diamond's higher refractive indexcreates a more diamond like appearance in part by reduction of whiteflash typically seen in CZ due to high dispersion. The diamond coatingalso leads to improvement in the preservation of facet edges due to thenanodiamond coating which provides abrasion resistance and finallyproviding protection from UV radiation that generally degrades the colorof the CZ over time.

In another embodiment of the invention, a thin film of nanocrystallinediamond is grown all around a cubic zirconia gem using a CVD techniquesuch as hot filament CVD diamond deposition technique in order to renderthe cubic zirconia with a skin of crystalline diamond having aparticular color appearance. The technique of CVD diamond growth or hotfilament CVD diamond deposition is known in the prior art, but theapplication of such processes to grow a diamond skin around a gemmaterial to render it with certain optical properties, is not discussedin the prior art.

In another embodiment of the invention nanocrystalline diamond particlesare applied as the filler media which is used to perform fracturefilling of natural diamonds or other non-diamond gemstones.

The invention, in one embodiment, describes a process to produce anano-crystalline diamond film on various substrates includingnon-diamond natural and synthetic gem materials. The substrates includethose that are naturally colored or color enhanced via treatments, orclear. The invention may be applied to other decorative objects such asglass or polymer substrates used in commercial applications or asdecorative objects, metal jewelry, metal decorative objects, eyeglasses,and eyeglass frames, watch articles such as the casing, crystal, glass,dial, strap etc. In one embodiment of the invention, the nanocrystalinediamond coating is applied to faceted cubic zirconia to improve thephysical characteristics of the substrate to make it appear more diamondlike and to improve its physical qualities in the areas of, for example,abrasion resistance.

The term “Nanodiamond” is broadly used herein to describe a variety ofdiamond based materials at the nanoscale including but not limited topurephase diamond films, diamond particles and their structuralassemblies.

Nanodiamond particles can be synthesized using various techniques suchas detonation synthesis or chemical vapor deposition processes. [4.Ultrananocrystalline Diamond: Synthesis, properties and Applications,edited by D.Gruen, A.Vul and O.Shenderova, NATO Science Series, KluwerAcad.Publ., 2005]

Nanodiamond particles are available commercially in powder form ordispersed in oils, solvents or water. The diamond purity and surfacechemistry of the nanodiamond particles in various dispersion media varyfrom vendor to vendor.

In one embodiment, the invention uses commercially available Nanodiamondpowders suspended in appropriate dispersion media. The synthesis of thenanodiamond particles can be accomplished by various techniques that areknown in the prior art. Nanodiamond synthesis was discovered in the USSRthree times over 19 years: first by K. V. Volkov, V. V. Danilenko, andV. I. Elin at the VNIITF (Snezhinsk) in 1963 and then, in 1982, by A. M.Stayer and A. I. Lyamkin at the Institute of Hydrodynamics, SiberianDivision, Academy of Sciences of the USSR (Novosibirsk), and by G. I.Savvakin at the Institute of Problems of Materials Science, Academy ofSciences of the UkSSR (Kiev). All of these researchers discoverednanodiamond synthesis accidentally while studying diamond synthesis byshock compression of nondiamond carbon modifications in blast chambers.

One class of nanodiamond material in which the characteristic size ofthe basic diamond constituents encompassing the range of just a fewnanometers. Within this class of materials, nanodiamond synthesized fromcarbon contained in the molecules of explosives by detonation of theexplosive is called detonation nanodiamond (DND). [Ref:Dolmatov, V. Y.,Detonation synthesis ultradispersed diamonds: properties andapplications, Russian Chemical Reviews, 70, 607, 2001]. Detonationnanodiamond is one source of nanodiamond that can be used in theprocedures of the present invention.

DND materials possess different degrees of diamond purity depending onthe method of purification of the detonation soot obtained after theexplosion.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a faceted gem being immersed in ananodiamond slurry in accordance with the present invention;

FIG. 2 is a micrograph view of gemstone pavilion facets which have beencoated with a nanodiamond slurry;

FIG. 3 is a high resolution transmission electron micrograph ofnanodiamond clusters in accordance with the invention;

FIG. 4 is a lattice image of a nanodiamond particle in accordance withthe invention;

FIG. 5 is a graph of XPS data on nanodiamond;

FIG. 6 is a schematic view of a plasma ion-assisted deposition systemused for depositing an optically transparent high quality DLC on varioussubstrates layer of oxides, nitrides, oxynitrides of various transitionmetals or a combination thereof;

FIG. 7 is a scanning electron microscope image of nanodiamond coating ona gem surface;

FIG. 8 is a high magnification scanning electron microscope image of agem surface coated with nanodiamond film;

FIG. 9 is a transmission electron microscope cross sectional view of ananodiamond coating on a gem surface;

FIG. 10 is a high resolution image of nanodiamond particles with alattice spacing consistent with diamond coating on a gem surface; and

FIG. 11 is a schematic view of a diamond that has been filled withnanocrystalline diamond particles in accordance with the invention.

DETAILED DESCRIPTION OF THE DRAWINGS

The procedure outlined below provides the step-by-step method to producethe nano-crystalline diamond coating according to one embodiment of theinvention:

1. Commercially obtained nanodiamond powders are used to prepare aslurry in a solvent media such as dimethyl sulfoxide (DMSO), ethanol orpreparation of functionalized nanodiamond with improved solubility inpolar organic solvents such as alcohols or tetrahydrofuran (THF).Functionalized nanodiamonds are prepared by its reactions withalkylithium reagents, diamines and amino acids. [Functionalization ofNanoscale Diamond Powder: Fluoro-, Alkyl-, Amino-, and AminoAcid-Nanodiamond Derivatives, Yu Liu, Zhenning Gu, John L. Margrave,†and Valery N. Khabashesku* Chem. Mater., 2004, 16 (20), pp 3924-393. Thechoice of nanodiamond powder is based upon the size of nanodiamondparticle desired in the nanodiamond coating and varies from 5-20 nmsized powders to several 100 nm sized powders. In one embodiment of theinvention, powders containing nanodiamond less than 100 nm in size areused for the nanodiamond coating.

2. A mixture of Nanodiamond slurry with methanol (or ethanol or IPA) asdiluents is prepared.

3. The substrate intended for nano-crystalline diamond coating isimmersed in the mixture (FIG. 1).

4. Sonication is performed in a regular sonic bath for a duration thatis optimized via experimentation for various substrates. In the case ofsonication of faceted gems in the nanodiamond slurry the sonication timeis typically 10-30 minutes. The duration of the sonication is derivedexperimentally by performing the sonication of the object to be coatedwith nanodiamond for various durations and examining the objects usinganalytical techniques such as electron microscopy. A sonic bath is apiece of industrial or laboratory equipment that includes a container,or bath, used for cleaning, or mixing things inserted into the bath, byapplication of ultrasonic vibrations through the liquid in the bath.There are several commercially available ultrasonic bath systems whichvary in their ability to apply ultrasonic energy by ultrasound frequency(15-400 kHz).

5. Remove the substrate from the mixture and quickly rinse with solventto avoid formation of big agglomerates.

6. After rinsing with solvent the treated substrate is dried withnitrogen flow or the flow of another inert gas. The resulting coatingconsists of highly adherent Nanodiamond particles that are held in placeby van der Waal's forces. FIG. 2 depicts micrographs of nanocrystallinediamond particles using high resolution transmission electron microscopy(HRTEM). FIG. 5 depicts X-ray photoelectron spectroscopy (XPS) data ofnanodiamond material.

7. The nano-crystalline diamond coated substrate is placed under vacuumin an ion-assisted plasma deposition system such as that depicted inFIG. 6.

8. A thin optically transparent film of DLC is deposited on thenano-crystalline diamond coated substrate to further stabilize thehighly adherent layer. The deposition parameters are chosen so as toallow an optimum thickness of DLC film containing high percentage of sp3bonds and optical transparency to be deposited. Optimum thickness in oneexample embodiment is about thirty nanometers. Alternatively, thenanocrystalline diamond coated substrate may be stabilized withdeposition of an oxide or nitride of various metallic or non-metallicspecies using the ion-assisted plasma deposition system depicted in FIG.4. Oxides, Nitrides and/or Oxy-nitrides may be chosen from any of theseries of transition metals and may be selected from a group of metalsincluding but not limited to Zinc, Titanium, Titanium-Aluminum, Silicon,Yttrium, Silver, Platinum, Gold, Zirconium or Tantalum. These coatingsmay be used in conjunction with the deposition of a DLC coating or usedwithout the DLC coating.

Diamond-like-carbon (DLC) coatings are formed when ionized anddecomposed carbon or hydrocarbon species land on the surface of asubstrate with energy typically 10-300 eV. DLC films may possessexceptional mechanical, optical, electrical, chemical and tribologicalproperties and can be deposited at low substrate temperature (<200° C.).DLC film properties include high hardness, high optical band gap andhigh electrical resistivity. They generally are inert and demonstratelow friction and wear coefficients.

Such films are generally amorphous (i.e have no dominant crystallinelattice structure) and consist of a mixture of sp2 (trigonalstructuring—graphite) & sp3 (tetrahedral structuring—diamond) phases.The sp3/sp2 ratio of the DLC film is controlled by the conditions of thedeposition including but not limited to the chamber pressure, gas flowrate, and voltage.

In another example embodiment to create nanocrystalline diamond coatingon a gem or other media the following procedure can be followed:

1. A Nanodiamond slurry is prepared by dispersing nanodiamond particlesin a solgel media. The composition of the solgel media is optimizedaccording to the substrate to be coated. In an example embodiment of theinvention solgels in oxides of Zinc, Titanium, Silicon, or Aluminum isused to create a composite film of nanodiamond particles.

2. The substrate intended for nanocrystalline diamond coating isimmersed in the Nanodiamond solgel for a duration that is optimized byexperimentation for various substrates according to the desired densityof the composite film, adhesion to the substrate material, and desiredappearance.

3. The substrate is removed from the Nanodiamond solgel and dried withnitrogen flow or the flow of another inert gas. The composition of theSolgel media is optimized to achieve curing via volatilization of theorganic component via a low temperature (<150C) or room temperaturecure.

4. The resulting coating consists of a matrix of Nanodiamond particlesdispersed in the solgel media that adheres to the substrate.

The solgel based nano-crystalline diamond slurry as described above canbe used on objects such as jewelry eyewear or other decorative objectsto provide protection from oxidation, corrosion and/or abrasion andadditionally, in some cases, can be used to impart color to the objector to provide the coated object with the ability to block UV radiation.

The procedure outlined below provides a step-by-step method to producethe nanocrystalline diamond coating according to another embodiment ofthe invention:

1. Prepare a mixture of Nanodiamond slurry with, for example, methanol(or ethanol or isopropyl alcohol) as diluent. The nanodiamond slurryconsists of nanodiamond particle such as DND particles dispersed inwater based or solvent based media. Solvent based media may includeother organic solvents. It is helpful if the slurry is prepared so thatthe nanodiamond particles remain in suspension for the duration of theprocedure.

2. Immerse the substrate intended for nanocrystalline diamond coatinginto the nanodiamond slurry mixture (FIG. 1).

3. Perform sonication in a regular sonic bath for a duration that can beoptimized via experimentation for various substrates. Sonication may beaccomplished by placing a vessel containing the substrate andnanodiamond slurry contained in a vessel into a water bath in anultrasound unit.

4. Remove the substrate from the mixture and quickly rinse with solventto avoid formation of big agglomerates. Acetone and isopropanol can beused in sequence for this purpose.

5. After rinsing with solvent dry with a flow of inert gas such asnitrogen. The drying can also be accomplished with another inert gassuch as argon. The resulting coating consists of highly adherentnanodiamond particles that are held in place by van der Waal's forces.FIGS. 2, 2 a and 2 b depict micrographs of the nanocrystalline diamondparticles using high resolution transmission electron microscopy(HRTEM). FIG. 5 shows X-ray photoelectron spectroscopy (XPS) data of DNDmaterial.

6. The nano-crystalline diamond coated substrate is placed under vacuumin an ion-assisted plasma deposition system (FIG. 6). An exampleappropriate ion-assisted plasma deposition system is described in a U.S.Published Patent Application 2006/0182883 the contents of which areincorporated by reference herein.

7. A thin optically transparent film of, for example DLC or zinc oxideis deposited on the nano-crystalline diamond coated substrate to furtherstabilize the highly adherent layer. The deposition parameters arechosen so as to allow an optimum thickness of DLC film containing highpercentage of sp3 bonds and optical transparency to be deposited. A highpercentage of sp3 bonds in this context may be about seventy percent butmay vary depending on the application. Generally, a higher concentrationof sp3 bonds leads to a harder coating but a higher percentage of sp3bonds may interfere with optical transparency or clarity. Alternatively,the nanocrystalline diamond coated substrate may be stabilized withdeposition of an oxide, nitride or various metallic or non-metallicspecies using the ion-assisted plasma deposition system shown in FIG. 6.Example Oxides include but are not limited to e.g. SiO₂, TiO₂, Al₂O₃,V₂O₃, Fe₂O₃, Cr₂O₃, NiO, Ta₂O₅. Example Nitrides include but are notlimited to e.g., TiN_(X), ZrN, TaN. Examples of other coating speciesinclude but are not limited to TiZrN, TiCN, TiC_(x)N_(y), ZrC_(x)N_(y),Au, Ag and Cu.

Procedure to create nano-crystalline diamond coating on a gem or othermedia in another embodiment of the invention:

1. The Nanodiamond slurry is prepared by dispersing DND particles in asol-gel media. The composition of the sol-gel media is optimizedaccording to the substrate to be coated.

2. Immerse the substrate intended for nano-crystalline diamond coatingin the Nanodiamond sol-gel for a duration that is optimized byexperimentation for various substrates.

3. Remove substrate from Nanodiamond sol-gel and dry with nitrogen flowor a flow of another inert gas. The composition of the sol-gel media isoptimized to achieve curing via volatilization of the organic componentvia a low temperature or room temperature cure. This can be done by theuse of organic solvents that are volatile at room temperature.

4. The resulting coating consists of a matrix of Nanodiamond particlesdispersed in the sol-gel media that adheres to the substrate.

The sol-gel based nanocrystalline diamond slurry as described above canbe used on objects such as jewelry eyewear, watches or other decorativeobjects to provide protection from oxidation, corrosion and/or abrasionand, additionally in some cases, be use to impart color to the object orprovide the coated object with the ability to block UV radiation.

Example procedure for fracture filling of diamonds with Nanodiamond inanother embodiment of the invention:

1. The Nanodiamond slurry is prepared by dispersing DND particles in achemically functionalized carrier media. The carrier media has avolatile component which easily evaporates at room temperature orelevated temperature and atmospheric pressure leaving behind aninorganic compound of oxide origin. The carrier media can be chemicallyfunctionalized in that components of the media may be chemicallyreactive in the formation of the fracture filling or in that portions ofthe media remain as part of the coating or filling.

2. Pre-clean the diamond (containing fractures that are open to thesurface) with solvents including alcohol, acetone, sulfuric acid,hydrogen peroxide, and/or water, to remove surface oils, hydrocarbonsand other common surface impurities therefrom.

3. Ensure that the fractures in the diamond are open to the surface byperforming laser drilling if necessary. Laser drilling may beaccomplished by the use of commercially available diamond laser drillingtechniques.

4. Perform cleaning in strong caustics and acids with rinses in between.This assists in the removal of any oxides or glassy structures, and/ormetallic traces in the diamond. The caustics or acids may include, forexample, sodium hydroxide, hydrofluoric acid, nitric acid, sulfuricacid, hydrochloric acid as well as other inorganic acids and alkalis.

5. The cleaned diamond is immersed in the Chemically FunctionalizedNanodiamond slurry placed in a pressure chamber maintained above 50atmospheres. In some applications it may be beneficial to utilizecentrifugal force to facilitate filling of the fractures.

6. The diamond is removed from pressure chamber after a durationoptimized according to the characteristics of the fractures beingfilled. The required duration may be affected by the depth, width,volume or shape of the fracture to be filled.

7. The diamond is sonicated in a solvent and dried in a nitrogen flow orthe flow of another inert gas (FIG. 5).

In another embodiment of the invention, the following procedure is used.

1. The Nanodiamond slurry is prepared by dispersing nanodiamondparticles in an appropriate carrier media such as DMSO which is furtherdiluted using other volatile organics such as methanol, ethanol or THF.The carrier media is volatile in nature and easily evaporates atelevated temperature and atmospheric pressure leaving behind thenanodiamond particles.

2. Pre-clean the diamond (containing fractures that are open to thesurface) with solvents including alcohol, acetone, sulfuric acid,hydrogen peroxide, and/or water, to remove surface oils, hydrocarbonsand other common surface impurities.

3. Ensure that the fractures in the diamond are open to the surface byperforming laser drilling, if necessary.

4. Perform cleaning in strong caustics and acids with rinses in between.This ensures removal of any oxides or glassy structures, and/or metallictraces in the diamond.

5. The cleaned diamond is immersed in the container of Nanodiamondslurry and placed in a pressure chamber maintained above 50 atmospheres.Unlike conventional fracture filling treatments using proprietaryformulations of molten glass the diamond does not need to be exposed toelevated temperature.

6. The diamond is removed from pressure chamber after a time periodoptimized according to the characteristics of the fractures beingfilled. The fractures that have very little depth into the diamond willfill up with the nanodiamond slurry in a shorter duration (1-4 hrs) anddiamonds having fractures that extend deep into the body of the stonemay need to remain in the pressure vessel to promote the filling of thefractures for durations greater than 8 hours.

7. The diamond is sonicated in a solvent and dried in a nitrogen flow(FIG. 5).

8. In another embodiment of the invention centrifugal force is used forthe filling of the fractures using the hydrostatic force generated andthe rotational speed of the system is optimized according to the filllength of the fractures.

An example procedure for filling of fractures and fissures in emeraldwith sol gel media containing a dispersion of nanodiamond particles ispresented below. Emerald has a mineral composition Al2Be3[Si6O18] whichcomes from a class of aluminosilicates. Unlike the use of foreignmaterials such as oils or polymers, the filling of fractures in emeraldsby materials that have the same or similar composition as the emeraldshould enable a superior quality filling that will not have thedisadvantages of conventional fillings. A sol gel media containing aninorganic component from the class of aluminosilicates close incomposition to the emerald mineral, and mixed with a chemicallyfunctionalized nanodiamond slurry containing a volatile organiccomponent is chosen.

1. The Nanodiamond Emerald Sol Gel slurry is prepared by dispersingnanodiamond particles in an appropriate carrier media such as DMSO whichis further diluted using other volatile organic liquids such asmethanol, ethanol or THF and further mixing it with an aluminosilcatesol gel (commercial formulations with composition close to emeraldmineral).

2. Pre-clean the emerald (containing fractures that are open to thesurface) with solvents including alcohol, acetone to remove surfaceoils, hydrocarbons and other common surface impurities.

3. Ensure that the fractures in the emerald are open to the surface byperforming mechanical drilling or laser drilling, if necessary, andperform cleaning using solvents.

4. The cleaned emerald is immersed in a container containing theNanodiamond Emerald sol gel slurry and placed in a pressure chambermaintained above 50 atmospheres.

5. The emerald is removed from pressure chamber after a durationoptimized according to the characteristics of the fractures beingfilled. The fractures that have very little depth into the emerald willfill up with the nanodiamond emerald solgel slurry in a shorter duration(1-4 hrs) and emeralds having fractures that extend deep into the bodyof the stone will need to remain in the pressure vessel to promote thefilling of the fractures for durations greater than 8 hours.

6. The emerald is sonicated in a solvent and dried in a nitrogen flow orflow of other inert gas (FIG. 5).

7. In another embodiment of the invention a centrifugal force is usedfor the filling of the fractures using the hydrostatic force generatedand the rotational speed of the system is optimized according to thefill length of the fractures.

In accordance with the invention a sol gel liquid of a composition thatis the same or similar to the emerald mineral is mixed with ananodiamond slurry and when the pressure filling technique ofcentrifugal or pressure chamber is applied, the slurry moves into thefractures and fissures aided by the movement of the nanodiamondparticles. IN this embodiment of the invention, the nanodiamondparticles serve the purpose of improving transport properties of theliquid and also help in immobilizing the cured sol after the organiccomponent is volatilized. It is known that nanoparticles dispersedcomposite materials are strong and adhere well when applied as a coatingmaterial.

Fluid filling of microchannels can be done in various methods includingbut not limited to mechanical pressure (such as the pressure chamberdescribed above), electrical force (electrohydrodynamic flow,electrophoretic flow and electroosmotic flow [1]), surface tension,centrifugal force etc [2]. Ref 1 : Fuhr, G.; Schnelle, T.; Wagner, B.,“Travelling wave-driven microfabricated electrohydrodynamic pumps forliquids”, Journal of Micromechanics and Microengineering, 4 (1994):217-26).Ref 2: Microfluidics of Complex Fluids, Kai Kang, Ph. D.Dissertation, Ohio State University, 2003.

The resulting fracture filled diamond and/or fracture containingnanocrystalline diamond with or without other carrier or solgel media,provide several advantages over existing methods:

1. The refractive index of the diamond filling is the same as thediamond or nearly so if any carrier media or solgel media is used. Thisshould make the filled area undetectable or nearly so.

2. The fracture filled emerald contains the material of same or similarcomposition as the emerald mineral along with the dispersed nanodiamondparticles. This renders the filled fractures undetectable or nearly so,additionally provides superior mechanical and thermal stability to thegem rendering it the ability to be set in jewelry employing variousmethods such as wax setting which typically is not done for emeralds.Emeralds by themselves can withstand elevated temperatures encounteredin some jewelry setting operations such as wax setting, but the fillingssuch as oils, resins and polymers used to fill fissures and crackscannot withstand elevated temperatures and thus emerald is always handset very carefully. The method disclosed in this invention wherein theemerald is filled with a material of the same or similar composition asthe mineral itself and further stabilized by the dispersion ofnanodiamond particles provides new abilities for this gem to withstandenvironments of jewelry setting as well as end user handling thattypically cannot be done by emeralds that are filled using conventionalforeign materials. This process allows the emerald to be healed of itsfractures and fissures rather than just filled.

3. The fillings in diamond or emerald cannot be removed by exposure toacids or caustics or solvents unlike conventional glass fillings fordiamonds that can be attacked by acids and caustics as well asconventional fillings for emeralds which can be removed by solvents orsteam.

4. The nanocrystalline diamond filling consists of the agglomerates ofthe sub-5 nm diamond particles integrated in the carrier matrix and donot have a tendency to migrate once the volatile component of thecarrier media has been removed.

A diamond that is to undergo fracture filling using nano-crystallinediamond particles as the filler material, should be inspected to verifyif the fractures to be filled reach the surface. If the fractures orother flaws such as inclusions are present in the interior of the stonewith no path to the surface then the diamond may undergo the laserdrilling process to create an opening or nanotubule to the fracture orinclusion. The laser drilling technique is described in the prior artand is a commercially available process.

The combustibility of diamond has allowed the development of laserdrilling techniques which, on a microscopic scale, are able toselectively target and either remove or significantly reduce thevisibility of crystal or iron oxide-stained fracture inclusions.Diamonds have been laser-drilled since at least the mid-1980s.

Laser drilling involves the use of an infrared laser (wavelength about1060 nm) to bore very fine holes (less than 0.2 millimeters or 0.005inches in diameter) into a diamond to create a route of access to aninclusion. Because diamond is transparent to the wavelength of the laserbeam, a coating of amorphous carbon or other energy-absorbent substanceis applied to the surface of the diamond to initiate the drillingprocess. The laser then burns a narrow tube to the inclusion. Once theincluded crystal has been reached by the drill, the diamond is immersedin sulfuric acid to dissolve the crystal or iron oxide staining Thisprocess is not effective for inclusions which are diamonds themselves,as diamond is not soluble in sulfuric acid).

Several inclusions can be thus removed from the same diamond, and undermicroscopic inspection the fine bore holes are readily detectable. Theyare whitish and more or less straight, but may change directionslightly, and are often described as having a “wrinkled” appearance. Inreflected light, the surface-reaching holes can be seen as dark circlesbreaching the diamond's facets. The diamond material removed during thedrilling process is destroyed, and is often replaced with glassinfilling, using the fracture filling techniques known in the prior artsuch as the Yehuda Treatment or the Koss process (Ref: Fracture Fillingof Diamonds, Janina Skawinska A. G. (C.I.G.), Winnipeg, Man).

If the flaw is an inclusion then after laser drilling procedure thediamonds are deep boiled using acids (sulfuric, nitric, hydrofluoricacids) to remove the impurities or foreign substances that make up theinclusion.

The diamond containing the flaw (fracture or void from which inclusionshave been removed) is then cleaned using Acetone and IPA solventcleaning procedures in a sonic bath and thereafter placed into fixturesor specially designed vessels that contain the nanocrystalline diamondfiller media. The nanocrystalline diamond filler media includesnanocrystalline diamond particle clusters suspended in various mediaincluding but not limited to distilled water, dimethyl sulfoxide,dimethylformamide, dimethylacetamide, methanol, etc. In one embodimentof the invention, the diamond submerged in the nanocrystalline diamondmedia containing vessel is placed inside a pressure vessel capable ofapplying pressures up to 50 atmospheres.

The resulting fracture filled diamond, containing nanocrystallinediamond, provides several advantages over the product of existingmethods.

1. The refractive index of the diamond filling is the same as thediamond.

2. The filling cannot be removed by exposure to heat or acids sinceneither affect the nanocrystalline diamond particles unlike in the caseof the glass-like fillings.

The nanocrystalline diamond filling consists of the agglomerates of thesub-5 nm diamond particles integrated in the carrier matrix and do nothave a tendency to migrate once the volatile component of the carriermedia has been removed.

The sol-gel process is a versatile solution process for making ceramicand glass materials. In general, the sol-gel process involves thetransition of a system from a liquid “sol” (mostly colloidal) into asolid “gel” phase. Applying the sol-gel process, it is possible tofabricate ceramic or glass materials in a wide variety of forms:ultra-fine or spherical shaped powders, thin film coatings, ceramicfibers, microporous inorganic membranes, monolithic ceramics andglasses, or extremely porous aerogel materials.

The starting materials used in the preparation of the “sol” are usuallyinorganic metal salts or metal organic compounds such as metalalkoxides. In a typical sol-gel process, the precursor is subjected to aseries of hydrolysis and polymerization reactions to form a colloidalsuspension, or a “sol”. Further processing of the “sol” enables one tomake ceramic materials in different forms. Thin films can be produced ona piece of substrate by spin-coating or dip-coating. When the “sol” iscast into a mold, a wet “gel” will form. With further drying andheat-treatment, the “gel” is converted into dense ceramic or glassarticles. If the liquid in a wet “gel” is removed under a supercriticalcondition, a highly porous and extremely low density material called“aerogel” is obtained. As the viscosity of a “sol” is adjusted into aproper viscosity range, ceramic fibers can be drawn from the “sol”.Ultra-fine and uniform ceramic powders are formed by precipitation,spray pyrolysis, or emulsion techniques.

FIGS. 5, 6 7 and 8 provide the data to illustrate the microscopicanalysis of a nanodiamond film deposited on a cubic zirconia gem surfaceusing the procedures described in the invention.

The procedure outlined below provides a method in accordance withanother embodiment of the invention to produce a nanocrystalline orpolycrystalline diamond conformal growth all over a faceted or unfacetedgem material that is capable of withstanding elevated temperaturerequired for diamond deposition using techniques such as hot filamentCVD.

1. The gem material such as a faceted cubic zirconia is pre-cleaned withsolvents including acetone and isopropyl alcohol (IPA) to remove surfacecontamination, dirt and oils. Place the cubic zirconia in a system asdescribed by FIG. 6 and deposit a thin seed layer of a materials such astitanium, graphite or silicon carbide (thickness sub-20 nm). This isdone to promote the adhesion of the CVD diamond film that is to be grownover the gemstone surface.

2. Load the gem material such as the faceted cubic zirconia or otherdecorative object onto a flat holder by placing the gemstone table-sidedown such that the pavilion side of the gem is exposed.

3. Load the holder into a commercially available diamond CVD system.

4. The chamber of the diamond deposition system is evacuated to below 20mTorr and the reaction gases comprising of methane (CH4) diluted withhydrogen(H2) are flowed into the system. The diamond deposition whileusing cooling systems to control the temperature of the holdercontaining the gemstones to below 750C.

5. The thickness of the diamond film grown on the exposed surface of thegemstone is controlled by the reaction chemistry and duration of the runso that resulting thickness is in the sub-100 nm range. The chemistry ofthe film is controlled by the sequence of hydrogen etching to remove thenon-diamond components of the film.

6. The gemstone is removed from the system after the deposition cycleand then reloaded onto another fixture that allows the stone to beplaced with the table side exposed.

7. The process of diamond deposition is again run in the diamond CVDsystem.

The invention in one embodiment includes depositing a thick layer of hotfilament CVD diamond on a material such as titanium or silicon carbideor molybdenum or tantalum to create a black diamond watch dial. Theprocedure in this embodiment is similar to how the gemstone is coated inthe CVD chamber except that the thickness is optimized to be 10-12microns in order to achieve a black color.

The present invention may be embodied in other specific forms withoutdeparting from the spirit of the essential attributes thereof;therefore, the illustrated embodiments should be considered in allrespects as illustrative and not restrictive, reference being made tothe appended claims rather than to the foregoing description to indicatethe scope of the invention.

1. (canceled)
 2. A method to apply nano-crystalline diamond onto aselected substrate, comprising preparing a nanodiamond slurry ofnanodiamond particles dispersed in a medium; immersing the selectedsubstrate in the nanodiamond slurry for a predetermined period of time;removing the substrate from the slurry; and drying the substrate andnanodiamond slurry that is adherent to the substrate with a flow ofinert gas whereby the substrate is left coated with a coating of thenanodiamond particles that are highly adherently held by van der Waalsforces.
 3. The method as claimed in claim 2, further comprisingperforming sonication of the selected substrate during or afterimmersion in the slurry.
 4. The method as claimed in claim 3, furthercomprising predetermining a duration of the sonication viaexperimentation for the selected substrate.
 5. The method as claimed inclaim 2, further comprising rinsing the substrate with solvent prior todrying the substrate with a flow on inert gas.
 6. The method as claimedin claim 2, further comprising: placing the selected substrate undervacuum in an ion assisted plasma deposition system; and depositing anoptically transparent film of diamond like carbon over the coating ofthe nanodiamond particles.
 7. The method as claimed in claim 2, furthercomprising: placing the selected substrate under vacuum in an ionassisted plasma deposition system; and depositing an oxide or nitridelayer over the coating of the nanodiamond particles.
 8. The method asclaimed in claim 2, further comprising selecting the medium in which thedetonation nanodiamond particles are dispersed to be a liquid.
 9. Themethod as claimed in claim 2, further comprising selecting the medium inwhich the detonation nanodiamond particles are dispersed to be a sol-gelmedium.
 10. The method as claimed in claim 2, further comprisingselecting the sol-gel medium to include an organic component that isvolatile at below 200C to facilitate curing by volatilization.
 11. Themethod as claimed in claim 2, further comprising selecting the medium inwhich the detonation nanodiamond particles are dispersed to be achemically functionalized carrier medium.
 12. The method as claimed inclaim 11, further comprising selecting the chemically functionalizedcarrier medium to include a volatile component and an inorganic oxide,the volatile component being selected to readily evaporate at ambientroom temperature or at elevated temperature and atmospheric pressure toleave behind the inorganic oxide.
 13. The method as claimed in claim 2,further comprising: selecting the selected substrate to have fracturesthat are open to the substrate surface; and precleaning the substratewith one or more cleaning agents.
 14. The method as claimed in claim 13,further comprising selecting the one or more cleaning agents from agroup consisting of alcohols, acetone, sulfuric acid, hydrogen peroxide,water and a combination of the foregoing.
 15. The method as claimed inclaim 13, further comprising: cleaning the substrate with strongcaustics or acids; and rinsing the substrate between cleaning thesubstrate with the strong caustics or acids.
 16. The method as claimedin claim 13, further comprising laser drilling, if necessary tofacilitate access to the fractures.
 17. The method as claimed in claim2, further comprising placing the selected substrate immersed in theslurry into a pressure chamber that can be maintained at above fiftyatmospheres pressure and pressurizing the pressure chamber to abovefifty atmospheres pressure.
 18. The method as claimed in claim 17,further comprising: removing the selected substrate from the slurry andthe pressure chamber; immersing the selected substrate in a solvent;sonicating the selected substrate in the solvent; removing the selectedsubstrate from the solvent; and drying the selected substrate in theflow of the inert gas following removal of the selected substrate fromthe solvent.
 19. The method as claimed in claim 2, further comprising:applying a layer of chemical vapor deposition diamond over the coatingof the nanodiamond particles using the coating of nanodiamond particlesas a seed layer.
 20. The method as claimed in claim 19, furthercomprising: placing the substrate with coating of the nanodiamondparticles in a chamber of a chemical vapor deposition system: evacuatingthe chamber to below 20 mTorr; and flowing reaction gases into thechamber including methane diluted with hydrogen.
 21. The method asclaimed in claim 2, further comprising: depositing a sub-20 nm layer oftitanium, titanium oxide, graphite or silicon carbide over thesubstrate.
 22. The method as claimed in claim 20, further comprising:selecting the substrate to be a gemstone having a table side and apavilion side; loading the gemstone onto a flat holder table side downsuch that the pavilion side of the gemstone is exposed; applying thelayer of chemical vapor deposition diamond to a thickness of less than100 nanometers to the exposed pavilion side; removing the gemstone fromthe flat holder; reloading the gemstone onto another fixture table sideup such that the table side of the gemstone is exposed; and applying thelayer of chemical vapor deposition diamond to a thickness of less than100 nanometers to the exposed table side.
 23. The method as claimed inclaim 20, further comprising: using cooling systems to maintain atemperature of the gemstone below 750 C.
 24. The method as claimed inclaim 20, further comprising: applying the layer of chemical vapordeposition diamond to a thickness of 10 to 12 microns to achieve a blackcolored coating.
 25. A method of filling fractures or fissures in anemerald, comprising: preparing a nanodiamond-emerald sol-gel slurry;precleaning the emerald with an organic solvent; immersing the emeraldin the nanodiamond-emerald sol gel slurry; subjecting the emeraldimmersed in the nanodiamond-emerald sol gel slurry to pressure abovefifty atmospheres or to centrifugal force; sonicating the emerald in asolvent; and drying the emerald flow of inert gas.
 26. The method asclaimed in claim 25, further comprising: preparing thenanodiamond-emerald sol gel slurry by dispersing nanodiamond particlesin a carrier medium; diluting the carrier medium containing thenanodiamond particles by the addition of a volatile organic liquid tocreate a diluted carrier medium containing the nanodiamond particles;mixing a sol gel medium containing an aluminosilicate with the dilutedcarrier medium.
 27. The method as claimed in claim 25, furthercomprising: ensuring that the fracture or fissure is open to a surfaceby mechanical or laser drilling.
 28. The method as claimed in claim 25,further comprising selecting the nanodiamond-emerald sol gel slurry toinclude a volatile component, the volatile component being selected toreadily evaporate at ambient room temperature or at elevatedtemperature.